Low temperature extrusion primer

ABSTRACT

A method of obtaining improved adhesion of extruded olefin polymer coating materials to packaging material substrates, involving the use of a hydrolyzed copolymer of an olefin and ester of an unsaturated alcohol, e.g., an ethylene-vinyl acetate copolymer, or isocyanate reaction product thereof, as an adhesion improving primer or tie coat which permits extrusion of the coating material onto the primed surface at a lower temperature than ordinarily required, resulting in a better bond of coating material to substrate than ordinarily obtained at those lower temperatures.

United States Patent [72] Inventors James J. Fuerholzer Crystal Lake; Neal G. Reddeman, Wauconda; Samuel Zweig, Skokie, all of 111. [21] Appl. No. 686,427 [22] Filed Nov. 29, 1967 [45] Patented Oct. 26, 1971 [73] Assignee Morton International, Inc.

[54] LOW TEMPERATURE EXTRUSION PRIMER 33 Claims, 2 Drawing Figs.

[52] U.S. Cl 161/190, 161/218,161/251, 161/252,161/254, 156/244, 156/331, 156/332, 260/859 [51] Int. Cl ..B32b 27/08, B32b 27/40 [50] Field oi Search 161/190, 252,254,218, 251,244; 156/332, 3311;260/859 [56] References Cited UNITED STATES PATENTS 3,024,216 3/1962 Smitmans et a1 260/859 2,341,398 3/1939 Strother et a1. 156/332 X POLYOLE FIN 2,543,229 2/1951 Chapman 161/254 X 2,909,443 10/1959 Wolinski 161/254 X 2,964,422 12/1960 Bergstedt et al. 117/76 3,067,085 12/1962 Limperos 161/254 X 3,232,789 2/1966 Pelzek et al... ll7/l38.8 3,264,272 8/1966 Rees 260/785 3,340,091 9/1967 Zweig 161/252 X 3,371,002 2/1963 Reddeman 161/247 X 3,453,173 7/1969 lsley et a1 161/190 Primary Examiner-John T, Goolkasian Assistant Examiner-C. B. Cosby Attorney-Hofgren, Wegner, Allen, Stellman & McCord SUBSTRATE LOW TEMPERATURE EXTRUSION PRIMER PATETEUUET 26 I971 3,616,191

FIGI

POLYOLEFIN RESIN DRYING ZONE ,EXTRUDER POLYOLEFIN FILM SUBSTRATE CHILL ROLL POLYOLEFIN //-LOW TEMPERATURE Z SUBSTRATE INVENTORS. JAMES J. FUERHOLZER NEAL G. REDDEMAN SAMUEL ZWEIG BY $4 g wbuwxwmm M ATTORNEYS.

ll LOW TEMPERATURE EXTRUSION PRIMER BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to methods of coating substrates with olefin polymer materials which are normally difficult to secure to a substrate by applying from a hot melt without encountering oxidative deterioration of the coating material.

2. Description of the Prior Art Conventional hot melt coating processes are used to coat packaging material substrates, e.g., paper, paper board, aluminum foil, cellophane, nylon, and the like, with such olefin polymers as polyethylene, for the purpose of imparting heat seal properties, grease resistance properties and moisture barrier properties to the packaging material. For example, in one form of hot melt coating, i.e., an extrusion coating process, polyethylene coating material is heated to a temperature high enough tocause formation of a viscous fluid and is extruded from the viscous fluid state through a die onto the substrate. Alternatively, hot melt coating can be conducted by applying the viscous fluid or polymer melt by means of roller coating, flow coating, calendering, or spraying operations.

Many of the coating materials which are desirable 'for imparting the heat-seal and moisture barrier properties to a substrate are difficult to apply by using hot-melt processes. For example, in the case of olefin polymers such as polyethylene and copolymers of ethylene, it is necessary to heat the polymer melt to a very high temperature, e.g., above about 575 F. for polyethylene, before the coating material will adhere adequately to the substrate. This is true even when conventional primers areused on the substrate. At such high temperatures, olefin polymers are oxidized with concomitant thermal degradation of the polymer, e.g., by depolymerization and/or an objectionable amount of cross-linking. Oxidation is required to increase functionality or polarity of the material to obtain a reasonable bond of the polyolefin to the substrate; however the oxidation also introduces undesirable properties. For example, a characteristic objectionable ofi odor is produced which creates a serious problem in using the resulting laminate as a food packaging material; such oft odors are absorbed by the packaged food product. Another objectionable characteristic of the coating material which has been heated to such elevated and oxidizing temperatures is an increase in the temperature required for heat sealing. Additionally, use of higher temperature melts for coating limits the type of substrate which can be coated with the coating material since the substrate must be able to resist the adverse effects of the higher temperatures.

Even further disadvantages can result from high-tempera ture extrusion as practiced heretofore. For example, where polyethylene is used as the coating material, the high-temperature extrusion results in the formation of objectionable volatile decomposition products in the vicinity of the extruder and this presents problems of quality control and equipment maintenance. Also, in the case of polyethylene, films are sometimes difficult to secure to substrates even when using the high-temperature extrusion, especially when the extruded film thickness is about two mils or less; the thinner films have less heat-holding capacity and the lesser heat-holding capacity conversely requires higher extrusion temperatures to compensate therefor and this further compounds the high temperature odor problem and general deterioration of the extruded coating material. Additionally, higher processing web speeds used for economical production also require increased extrusion temperatures, again with undue oxidation and malodor.

Where such ester-containing copolymers as ethylene-vinyl acetate copolymers are used as coating materials, the presence of the ester group apparently lowers the temperature at which the undesirable odors are produced by decomposition or degradation. As the ester content is increased in such copolymers, the desirable extrusion temperature limit is further decreased. Thus, in spite of the polar nature of such copolymers, it has been difficult to bond them with good bonding strength to packaging substrates and the polymer decomposition and odor problem prevails.

The heat required for adhesion of an untreated olefin polymer coating to a substrate at least approaches the temperatures at which odors result, usually by oxidation and/or decomposition of the polymer. The copolymers, containing significant amounts of ester groups, so far as is known, cannot be adhered to a substrate by extrusion or the like without encountering the problem of malodor because the minimum temperature required for satisfactory adhesion is at least about the same as the decomposition temperature at which the odors are produced. Where such polyolefins as untreated polyethylenes are used as coating materials, the extrusion temperatures are defined by a relatively narrow range and temperature control therefor is a serious problem; temperature control within the range is difficult because of the high processing speeds desired for economic commercial production and the limitation of the equipment, among other reasons.

Often, such olefin polymers as polyethylene, polypropylene, ethylene-vinyl acetate copolymer, etc., are mixed with waxes and the mixture is applied from a melt, but it is still difficult to obtain adherence of the coating to the substrate below the oxidation temperature of the olefin polymer component.

SUMMARY OF THE INVENTION The present invention provides a method which can be used to adhere an olefin polymer coating to a substrate from a melt at temperatures below those at which the olefin polymer of the coating material may become materially oxidized and/or decomposed and without requiring artificial oxidation of the surface. According to the present method, before applying the hot coating material, the surface of the substrate is primed with a hydrolyzed copolymer of an olefin and an ester of vinyl alcohol. A hot melt of the coating material is applied over the primer, but the coating material need not be heated to such extreme temperatures as will cause oxidation of the material. The resulting coated substrate is generally free from malodors which are produced by the elevated temperatures and the coated material is entirely acceptable as a packaging material. Additionally, the coating retains its heat-scalability and the method eliminates the quality control and equipment maintenance problems associated with production of volatile decomposition products in the vicinity of the coating equipment.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 of the drawing is a block flow diagram of equipment suitable for carrying but a preferred form of the process of this invention; and

FIG. 2 is an enlarged cross section of a laminate including a substrate which is primed and coated. with an olefin polymer coating in accordance with a preferred form of the invention.

FURTHER DESCRIPTION OF THE PREFERRED EMBODIMENT The hydrolyzed copolymer used as the primer in the method is a hydrolyzed copolymer of one or more olefinic monomers and one or more ester monomers. The olefin monomers are usually ethylene or propylene because of the availability of such copolymers, although it is contemplated that copolymers of any olefin, e.g., in the C to C, range or higher, such as butylene, isobutylene and l-hexene, can be used. The ester monomer is an ester of an acid and vinyl alcohol or substituted vinyl alcohoLespecially including the: analogues of vinyl alcohol. The olefin monomer and ester monomer are, of coiirse, copolymerizable to form the copolymer. The nature of the acid in the ester monomer is not believed to be critical because acid groups are removed during hydrolysis and if the acid groups are of a structure impairing any desired properties of the copolymer, the amount of acid groups present can be regulated initially or decreased by increased hydrolysis. Usually, the acid of such a copolymerizable ester will be of low molecular weight, and vinyl acetate is a particularly preferred ester. The useful copolymers are well known and some are commercially available.

In the method, the hydrolyzed copolymer is applied in an amount sufficient to improve the adhesion of the coating material to the substrate. Because only a very small amount of the hydrolyzed copolymer is needed to prime the surface, the copolymer is usually applied in a diluted form such as in solution in a suitable volatile solvent. For use in solution, the copolymer will usually contain at least 8 percent to 10 percent by weight units derived from the unsaturated ester since copolymers containing a lesser amount of such units are relatively insoluble. Also, copolymers containing over 50 percent by weight of the ester units do not have as good adhesive characteristics; the preferred hydrolyzed copolymer has no more than about 40 percent by weight ester units. Suitable volatile solvents for the hydrolyzed copolymer are well known in the art and include, among others, the aromatic hydrocarbon solvents such as toluene which is readily available.

One particular class of hydrolyzed copolymer has been found to be especially advantageous when used as the primer in the method of this invention. This is the hydrolyzed interpolymer of ethylene and vinyl acetate which is reported as having the empirical formula (C,H )x (C,I-I,OH)y (C l-I, OCOCHflz, in which x, y, and z are numbers, the ratio on a weight basis of x to y being within the range of form about 5:l to about 300:1, and the ratio of x to z being within the range of from about l:l to about :1. Alternatively or additionally, reaction products of the hydrolyzed interpolymers, e.g., from reaction with organic isocyanates, can be used especially to provide cross-linked reaction products which have enhanced resistance to solvent and chemical attack.

The process of the present invention involves coating a packaging substrate with the hydrolyzed copolymer or interpolymer primer and thereafter applying, from a hot melt, an olefin polymer coating material at a temperature appreciably lower than the oxidation temperature of the olefin polymer in the coating material.

In a preferred embodiment, the present invention comprises a method of adhering a polyethylene film or other olefin polymer coating material to a flexible packaging substrate to provide an improved polyethylene coated product. The substrate is first primed, e.g., by spraying, slushing, immersing, roller coating, or otherwise (a) applying a primer containing an interpolymer or isocyanate reaction product thereof wherein the interpolymer has the structure of (Cd-1 (CgHg 0H)y (C,H OCOCH)z wherein x, y, and z are numbers, the ratio on a weight basis of x to y being within the range of from about 30:l to about 70:l, and the ratio of x to z being within the range of from about M to about 10:1, and (b) after the surface is primed, the coating material is applied. Preferably this is by extruding onto the primed surface of the substrate a polyethylene melt so as to form a film having a thickness of from about 0.] to about 10 mils at a melt temperature significantly lower than the oxidation temperature of polyethylene and usually at a temperature less than about 575 F. as taken.

at the adapter or die lands of the extruder.

Any of the flexible wrapping materials commonly used in the packaging art are suitable substrates in the practice of this invention. Thus, for example, Kraft paper, paperboard, glassine, aluminum foil, polypropylene film, regenerated cellulose, polyamide film, polyester film such as for example Mylar, cellulose acetate, polyvinyl chloride, and polyvinylidene chloride are only exemplary of the many substrates which may be extrusion coated or hot melt coated by the use of the primers employed in the invention.

PREPARATION OF HYDROLYZED ETl-lYLENE-VINYL ACETATE COPOLYMERS The hydrolyzed interpolymers of the low temperature polyolefin extrusion primers are prepared by hydrolyzing ethylene-vinyl acetate copolymers, usually having a vinyl acetate content ranging on a weight basis from about 15 to about 50 percent. These ethylene-vinyl acetate copolymers are available commercially under a variety of trade names. Controlled hydrolysis of these copolymers may be carried out according to the following procedure to yield an interpolymer having virtually any desired degree of hydrolysis.

As a typical example of such preparation, a solvent mixture of 75 parts by volume of toluene and 25 parts by volume of isopropanol is neutralized with alcoholic potassium hydroxide to the phenolphthalein end point. Ethylene vinyl acetate copolymer is added to and dissolved in the neutralized solvent, with efficient stirring and warming to effect complete solution of the copolymer. The theoretical amount of aqueous sodium hydroxide is added to yield an interpolymer having the desired degree of hydrolysis. The reaction mixture is then heated to reflux temperature under continuous stirring until the completion of the reaction which is indicated by a change in color of the phenolphthalein indicator from pink to colorless. The solvents are then distilled from the reaction mixture until the temperature of the distillate vapor is about I00 C. At the end of the distillation the solids level of the reaction mixture is from about 30 to 35 percent. At this point, if desired, the hydrolyzed interpolymer may be isolated by precipitation with methanol. The precipitate can be washed free of impurities and dissolved in a solvent of choice. However, it has been found expedient not to isolate the hydrolyzed interpolymer but simply to dilute the reaction mixture with a suitable solvent such as toluene to a 10 percent solids content to form a convenient low temperature, extrusion primer-use solution. By this method, ethylene-vinyl acetate copolymers have been hydrolyzed such that from about 3 percent to about 40 percent of the acetate groups are replaced by hydroxyl groups, as desired.

PREPARATION OF INTERPOLYMER REACTION PRODUCTS The hydrolyzed ethylene-vinyl acetate interpolymers may be further reacted with other ingredients, usually an isocyanate, including diisocyanates and other polyisocyanates. The reaction with polyisocyanate provides cross-linked products which also serve as low temperature extrusion primers but have the further advantage of enhanced chemical resistance compared with the nonreacted interpolymers. Any isocyanate or isocyanate polymer, prepolymer or adduct having available isocyanate groups is useable for reaction with the hydrolyzed ethylene-vinyl acetate copolymers. By the way of example but not limitation, some of the operable diisocyanates including toluene diisocyanates, tetramethylene diisocyanate, hexamethylene diisocyanate and 4, 4, 2, 4', and 2,2'-diphenylmethane diisocyanate and adducts of these diisocyanates with diols, triols, and polyols derived from polyethers and polyesters and the like. Polyols of such adducts with di or poly-isocyanates include trimethylolpropane, trimethylolethane, glycerol, l,2,4-trihydroxybutane, triethanolamine, ethylene glycol, propanediol- I ,3, butanediol- 1,4, hexanediol, methylhexanediol, diethyleneglycol. polyethers, polyesters, and mixtures thereof.

COATING PROCEDURE By the use of the aforedescribed primers, it was found possible to carry out an olefin polymer extrusion coating process at temperatures as low as the flowing point of the particular coating resin or polymer being used, e.g., from about 375 F. to about 560 F. or higher or lower, depending on the coating resin being used. By "flowing point" is meant that temperature at which a resin is sufficiently mobile to flow through the lips of an extruder die and onto a substrate. Primer coating weights of from about O.l lb. to about 1.5 lb. per ream of 3,000 square feet of substrate are sufficient to anchor or bond olefin polymer films having a thickness of from about 0.1 to about 10 mils to packaging substrates. Bond strength measurements, hereinafter described, attest to the effectiveness of the TABLE I. Representative Suitable Polyethylenes Polymer No Density Melt Index I 0.9I 7 3.4 2 0.923 3,] 3 0.9l5 23.0 4 0.930 3.0 5 0.923 8.0 6 0.9 l 8 I The term "Melt Index is a standard measure of the melt viscosity of polyethylenes and is expressed as the number of grams flowing through a standard orifice in a unit oftime at a standard temperature and pressure.

Polymers I, 3. and 6 are in the low-density range but vary in melt index from very 'low to very high. Polymer 4 is an intermediate density branches polymer. near the upper end of the density range for commercial branched polyethylenes. The other polymers are intermediate to these in density.

The invention is applicable to coating with various other polyolefins such as polypropylene, polybutene, etc. copolymers of olefins such as ethylene or propylene with each other or with vinyl acetate. acrylic acid, methacrylic acid, methyl acrylate ethyl acrylate, isobutyl acrylate, vinyl chloride, methyl methacrylate, tetrafluoroethylene, butenel. or to coating with ionomer olefin copolymer resins such as ethylene-acrylic acid copolymers, or ethylene-ethyl acrylateacrylic acid terpolymers. and other olefinically unsaturated monomers respectively. all of which are included in the expression polyolefin or "polyolefin resin" as used herein in identifying the coating material The advantages of the invention are best realized when the film is a heat-scalable polymer film formed from a monomer consisting predominantly of a lower olefin, that is, an olefin having two, three. or four carbon atoms. While ordinarily branched chain. low density resins would be used, important advantages are realized with films of high-density resins, linear resins. and stereospecific resins. It 18 normal practice in the art to extrude these resins or melt temperatures in the range of from about 5 F to about 625 F. The use of the aforedescribed primers permits efi'icient extrusion coating by these resins at temperaturesas low as the flowing point of each resin.

Typical Extrusion Coating Process The extrusion coating process employed in the following examples of this invention may be more clearly understood by reference to FIG 1. The extruder there shown is surmounted by a hopper containing the polyolefin resin to be extruded. In this process the extruder melts and continuously applies a controlled amount of polyolefin resin directly onto the primed web or substrate being coated. As is seen, the substrate material is fed from a substrate roll to the primer application station where it receives a coating of primer. The primecoated substrate IS then passed through a drying zone to evaporate volatile solvents and thence over a combining roll where a curtain of extruded polyolefinic resin falls directly onto the primed substrate The polyolefin coats out on the substrate as the coating material and substrate pass through the nip formed by the combining roll and a chill roll whereby a polyolefin-coated substrate is formed. The coated substrate is then wound onto a take-up roll for storage as desired In addition to coating material temperature, other factors which influence the strength of the bond obtained in a polyolefin extrusion coating process are the temperature of the web surface, thethickness of the polyolefin film being applied, the length of the airgap between the lip of the extruder and the nip of the pressure rolls, and the rate of speed of the substrate as it comes polyolefin.

Proper web surface temperature can be maintained by using a web preheat roll in the web feed system. Cold air blasts in the vicinity of the airgap should be minimized. In many instances, minimizing the distance between the die lips and the into contact with the extruded nip is also helpful. The speed of the substrate web and the thickness of the polyolefin film can be adjusted to maximize bond strength in a given coating operation.

The examples. given below, which are illustrative and are not intended to limit the scope of this invention in any manner, clearly show the excellent adhesion of polyolefin films to a variety of substrates obtained by the use of the present low-temperature extrusion primers at temperatures significantly lower than the polyolefin oxidizing temperature.

In the examples enumerated below, unless otherwise indicated, the substrates were coated with a 10 percent solution of the copolymer in toluene to provide aprimer coating having a-coat weight of about 0.3 to 0.6 lbs. of solids per ream of the substrate surface. All coat weights are reported as lbs. solids .per ream, after vaporization of solvent. The primed sheets were then fed under an extruder die and coated with the polyolefin melt at a melt temperature of 490 F. or other temperature as indicative in the examples. The polyolefin coating material was applied at approximately a I mil. thickness from the extruder as a film.

The coated substrates were tested for tensile strength of the bond between the coating and substrate materials and these results are reported for the examples below. Usually the tests showed a tensile strength greater than 200 grams per inch. The tests were made after the coated substrates were permitted to age at ambient room temperature for 24 hours and/or 3 weeks or at other aging times as indicated in the re ported results. The tensile strength of the bond was determined by an 'Instron tensile tester which is conventionally used in thepackaging industry to determine bond strengths. Briefly, the tensile tester includes a pair of vertically opposed clamps or jaws, one for clamping the substrate and the other for clamping the coating. The lower jaw is secured to a moving crosshead which is driven away from the upper jaw at a constant rate of speed. The upper jaw is associated with an electronic device which detects and records the load applied in units of weight or the force required to break the bond. Unless otherwise indicated, the control was a coated substrate prepared in the same manner as the coated substrates of the invention with the exception that a polyethyleneimine primer was used in lieu of the hydrolyzed interpolymer primer. Polyethyleneimine is a conventional primer for use in high temperature extrusion processes, e.g., at the higher oxidation or decomposition temperature. Where a plurality of substrates is indicated as having been coated using the primer of the examples and only one control is reported, the reported control bond strength is the average bond strength for controls embodying all of the same substrates used in preparing the laminates of the invention in that example.

The illustrative examples include the following:

EXAMPLE I Ethylene-vinyl acetate copolymer of 82 percent by weight of ethylene and 18 percent by weight of vinyl acetate was hydrolyzed according to the aforedescribed hydrolysis procedure to provide hydrolyzed ethylene-vinyl acetate interpolymer having the following compositions respectively:

Percent Hydrol- Ethyl- Vinyl Vinyl Primer ysls ene acetate alcohol IV O 1 a 1 E/VAc is the ratio of ethylene (E) to vinyl acetate (V Ac). 2 EIVA 1s the ratio of ethylene (E) to vinyl alcohol (V A). 3 Control-polyethyleneimine.

The Instron tensile tester results are as reported in table I.

It is seen from the preceding results 6125i l Taprimer is necessary for adhesion and that 2. under the low-temperature conditions employed, the primers of this invention are remarkably effective whereas the widely used polyethyleneimine provides little or no adhesion.

EXAMPLE 4 An ethylene-vinyl acetate copolymer of 72 percent by weight of ethylene and 28 percent by weight of vinyl acetate was hydrolyzed as heretofore described to provide hydrolyzed ethylene-vinyl acetate interpolymer primers having the following compositions:

TABLE I (K Cellophane Substrate) Percent Hydrol- Ethyl- Vinyl Vinyl ysis one acetate alcohol E/VAc E/VA Bond Strength g./in.

No primer 0 0 Cannon 0 0 Each of the above hydrolyzed lnterpolymers was coated B 290 480 onto K cellophane, and thereafter subjected to the g 3;; :3: 25 polyethylene extrusion coating procedure to apply a E 450 a polyethylene coating of approximately 1 mil thickness at a F 225 polyethylene melt temperature of 490 F.

measurements n a TABLE 4 (K Cellophane Substrate) Bond Stren th in. EXAMPLE 2 g g/ Each of the hydrolyzed interpolymer primers of example 1 Primer 24 Hours 3 Weeks was coated onto glassine according to the method described above, and thereafter extrusion coated with polyethylene at No Prime, 0 0 490 F. The results of bond measurements appear in table 2. Control 0 0 n 220 TABLE 2 (Glassine Substrate) 1 2m has-.. t M J 315 41s Bond strength gJin. .measurements not made Primer 24 Hours 3 Weeks EXAMPLE 5 45 Each of the hydrolyzed interpolymer primers of example 4 8 g was coated onto glassine and thereafter extrusion coated with B 285 365 polyethylene at 490 F. The results of bond measurements apc 265 355 pear in table 5. o 380 300 E TABLE 5 (GLASSINE SUBSTRATE) F 370 555 Bond Strength g./in. measurements not made Primer 24 Hours 3 Weeks No Primer 0 0 Control 0 0 EXAMPLE 3 H 235 325 l 310 370 Each of the hydrolyzed interpolymer prlmers of example I J 445 47s was coated onto aluminum foil according to the method K 400 described above and thereafter extrusion coated with polyethylene at 490 F. The results of bond measurements ap- 6O EXAMPLE 6 pear in table 3.

TABLE 3 (Aluminum Foil Substrate) Each of the hydrolyzed interpolymer primers of example 4 was coated onto aluminum foil and thereafter extrusion coated with polyethylene at 490 F. The results of bond measurements appear in table 6 TABLE 6 (ALUMINUM FOIL) Bond Strength gjin.

Primer 24 Hours 3 Weeks No Primer 0 0 Control 0 0 Each of the hydrolyzed interpolymersof example 1 (there designated primers B, C, D, E, and F) was reacted with a polytetramethylene glycol toluene diisocyanate adduct by admixture' therewith in the proportion of 46 parts of a percent solution of theiadduct and 54 parts of a 10 percent solution of the hydrolyzed interpolymer. Each of. of isocyanate-reacted hydrolyzed interpolymer primers (designated B-R, C-R, D-R', E-R, and'F-R respectively) was coated onto K Cellophane to provide a coating weight of reacted primer from about 0.3 lb. to about 0.6 lb. per ream. Eachof the primed substrates was extrusion coated with polyethylene at a polyethylene melt temperature of 490 F: whereby a polyethylene coating of approximately I mil inthickness was bonded to each substrate. Each of the resulting laminates was tested as before for bond strength. The results are tabulated in table 7.

TABLE 7 (K CELLOPHANE SUBSTRATE) BondStrength E./in.

Primer 24 Hours 3 Weeks No Primer 0 0 Control 0 0. B-R 325 3!!) C-R 235 FT D-R 280 E-R l Z55 F-R 175 340 FT is Film Tear which indicates that the bond is stronger than the substrate Measurements not made Example 8 Each of the hydrolyzed interpolymers of example 7 was reacted as there described, coated onto glassine, and thereafter extrusion coated with polyethylene at 490 F. The results of bond measurements are set forth in table 8.

TABLE 8 (GLASSINE SUBSTRATE) Measurements not made 10 EXKM PTHE 9 Each of the hydrolyzed interpolymers of example 7 was reacted as there described, coated onto aluminum foil, and thereafter extrusion coated with polyethylene at 490 F. The

bond strength measurements of the resulting construction are tabulated in table 9.

TABLE 9 (Aluminum Foil Substrate) Bond Strength g./in.

Primer 24 Hours 3 Weeks No Primer 0 Control 0 0 B-R 515 625 C-R 520 D-R 450 640 E-R a F-R 515 Measurements not made EXAMPLE 10 Each of the hydrolyzed interpolymers of example 4 (there designated primers H, I, J, and K) was reacted with a polytetramethylene glycol toluene diisocyanate adduct. by admixture therewith in the proportion of 46 parts of a 10 percent toluene solution of the adduct and 54 parts of a 10 percent toluene solution of the hydrolyzed interpolymer. Each of the isocyanate reacted hydrolyzed interpolymer primers, designated H-R, l-R, and K-R, was coated onto K Cellophane. Each ofthe; coated substrates was extrusion-coated coated with polyethylene at a polyethylene melt temperature of 490 F. whereby a;polyethylene coating of approximately 1 mllthlckness was bonded to each substrate. The bond strength of each of the resulting structures appears in table 10.

TABLE 10 (K Cellophane Substrate) Bond Strength g./in.

The procedure of example 10 was followed except the substrate was glassine. The bond strength. of the resulting structure appears in table 1 1.

TABLE 1 l (Glassine Substrate) Bond Strength g./in.

Primer 24 Hours 3 Weeks No Primer 0 0 Control 0 0 H- R V 365 340 l-R 270 435 The procedure of example 10 was followed except the substrate was aluminum foil. The bond strength of the resulting structures are set forth in table 12.

TABLE 12 (Aluminum Foil Substrate) Bond Strength g./in.

Primer 24 Hours 3 Weeks No Primer 0 Control 0 0 H-R 370 315 l-R 380 455 J-R 430 445 K-R 335 315 EXAMPLE 13 A hydrolyzed ethylene-vinyl acetate interpolymer primer was provided having the following composition:

7: 56 k k Vinyl Vinyl Hydrolysis Ethylene Acetate Alcohol E/VAc E/VA This primer was coated on K Cellophane, Glassine, and aluminum foil respectively, at a coating weight ranging from about 0.3 to about 0.6 lb. per ream. Each of the coated substrates was extrusion coated with about 1 mil of polyethylene at a temperature of 490 F. Bond strength measurements for the resulting laminates are set forth in table 13.

TABLE 13 Bond Strength g./in.

Substrate 24 Hours 3 Weeks K Cellophane 410 Glassine 465 545 Aluminum Foil 575 400 Control 0 0 not measured EXAMPLE l4 The hydrolyzed interpolymer of example 13 was reacted with tetramethylene glycol toluene diisocyanate adduct by admixture therewith in the proportion of 46 parts of a percent toluene solution of the adduct and 54 parts of a 10 percent toluene solution of the hydrolyzed interpolymer. The isocyanate reacted primer was coated onto K Cellophane,

glassine, and aluminum foil respectively, and thereafter extrusion coated with polyethylene at a polyethylene melt temperature of 490 F. whereby a polyethylene coating of approximately l mil thickness was bonded to each substrate. The bond strength results are set forth in table 14.

TABLE 14 Bond Strength g./in.

Substrate 24 Hours 3 Weeks K Cellophane 285 340 Glassine 460 495 Aluminum Foil 470 450 EXAMPLE 15 The hydrolyzed ethylene-vinyl acetate interpolymer primer of example 13 was coated onto glassine and onto polyvinylidene chloride-coated polypropylene (available commercially under the trade name Clysar) at a coating weight of 0.50 lb. per ream respectively. Whenever primer is applied to Clysar herein, it is applied to the polyvinylidene surface. An ethylene vinyl-acetate copolymer of 82 percent ethylene and i8 percent vinyl acetate was extrusion coated onto the primed substrate at a melt temperature of 475 F. The bond strengths are set forth in table 15.

TABLE 15 Bond Strength (Ethylene-Vinyl Acetate Copolymer Coating) Substrate 24 Hours 2 Weeks Glassine 350 ST NS Clysar 250 590 ST ST-Substrate tear.

NS-Not Separable. It was not possible to separate the ethylene-vinyl acetate coating from the substrate EXAMPLE 16 The hydrolyzed ethylene-vinyl acetate interpolymer of example 13 was reacted with polymethyl-polyphenyl isocyanate by admixing 10 percent toluene solutions of each of the reactants in the proportions of 76 percent of hydrolyzed interpolymer and 24 percent of isocyanate. The isocyanate-reacted primer was coated onto glassine and Clysar respectively at a coating weight of 0.5 lb. per ream each. The coated substrate was extrusion coated with the same ethylene-vinyl acetate copolymer as described in example 15 at a melt temperature 475 F. The bond strengths are set forth in table 16.

TABLE 16 Bond Strength Substrate 24 Hours 2 Weeks Glassine 350 FT. NS Clysar I80 550 EXAMPLE 1? The hydrolyzed ethylene-vinyl acetate interpolymer primer of example 13 was coated onto glassine at a coating weight of 0.5 lb. per ream. Polypropylene was extrusion coated onto the coated substrate at a melt temperature of 560 F. The bond strength obtained was as follows:

BOND STRENGTH 48 Hours 2 Weeks Not Separable Not Separable It is noted that it is customary in the art to extrusion coat with polypropylene at a melt temperature of at least about 600 F.

EXAMPLE 18 The hydrolyzed ethylene-vinyl acetate interpolymer of example 13 was reacted with polytetramethylene glycol toluene BOND STRENGTH Substrate 24 Hours 3 Weeks Pouch Paper Fiber Tear 280 K Cellophane Substrate Tear I50 Polypropylene Substrate Tear Fiber Tear A Mylar Substrate Tear SW-Substrate Tear Clysar Substrate Tear no measurement made EXAMPLE 19 The hydrolyzed interpolymer of example 13 was reacted with tetramethylene glycol toluene diisocyanate adduct by admixture therewith in the proportion of 45.75 parts of percent toluene solution of the adduct and 54.25 parts of a 10 percent toluene solution of the hydrolyzed interpolymer. The isocyanate reacted primer was coated onto uncoated cellophane and the coated cellophane was thereafter extrusioncoated with polyethylene at a polyethylene melt temperature of 480 F. whereby a polyethylene coating of approximately 2 mils thickness was bonded to the substrate. The resultant structure was tested as before or bond strength with the results as set forth below:

BOND STRENGTH g-lin.

Substrate 1 Week 2 Weeks 4 Weeks 6 Weeks Uncoated Cellulphane 435 735 440 545 EXAMPLE 21 The iscocyanate reacted interpolymer of example 14 was coated onto nylon film at a coating weight of 0.55 lb./ream. An ethylene-vinyl acetate copolymer of 91 percent by weight of ethylene and 9 percent by weight ofvinyl acetate was extrusion coated onto the primer substrate at a melt temperature of 475 F. The bond strength of the resultant structure is set forth below:

BOND STRENGTH g./in.

Substrate 1 Day (24 Hours) l Month Nylon 950 860 EXAMPLE 22 The hydrolyzed interpolymer of example 13 was coated onto Mylar, aluminum foil, and K Cellophane respectively, at a coating weight of 0.5 lb./ream. Polypropylene was extrusion coated onto each of the primer substrates at a melt temperature of 560 F. The bond strength of each of the resultant structures is set forth below.

BOND STRENGTH g./in.

Substrate 2 Days I Week 2 Weeks Mylar l 400 280 Aluminum Foil 350 390 200 K Cellophane 285 360 270 EXAMPLE 23 The isocyanate reacted interpolymer of example 14 was coated onto uncoated Cellophane, aluminum foil and polyvinylidene chloride-coated nylon (available commercially under the trade name Capran 77K) respectively at a coating weight of 0.35 lb./ream. An ethylene-vinyl acetate copolymer of 82 percent of ethylene and 18 percent of vinyl acetate was extrusion coated onto each of the primed substrates at a melt temperature of 450." F. The bond strength of each of the resultant structures is set forth below:

55 BOND STRENGTH g./in. BOND STRENGTH g./in.

Substrate l Week 4 Weeks 6 Weeks Substrate initial 4 Hours 16 Hours Uncoated Cellophane FT 370 500 Uncoated Cellophane 80 320 360 Aluminum Foil I40 900 EXAMPLE 20 Capran 77x 640 1700 The hydrolyzed interpolymer of example 13 was reacted 5 with polymethylene polyphenyl isocyanate by admixture EXAMPLE 24 therewith in the proportion of 10.4 parts of a 10 percent toluene solution of the isocyanate and 89.6 parts of a 10 percent toluene solution of the hydrolyzed interpolymer. The isocyanate reacted primer was coated onto uncoated cellophane and the primed cellophane was thereafter extrusion coated with polyethylene at a polyethylene melt temperature of 480 F. whereby a polyethylene coating of approximately 2 mils was bonded to the substrate. The resultant structure was tested for bond strength with the results as set forth below:

bond strength of each of the resultant structures is set forth below:

15 16 BOND STRENGTH g./in. Table Continued Substrate Aluminum Foil 250 280 130 Hours Control O 77K Although polyethyleneimine, a commercially used primer, NS was used as the control in the above examples, controls were also prepared substituting a nonhydrolyzed version of the hydrolyzed interpolymer for the'hydrolyzed interpolymer. The EXAMPLE 25 hydrolyzed interpolymer almost invariably gave a marked im- The following hot melt compositions, designated HMA, Rrovemem on the-order of 50 to 300 grams Per inch in f HM B, M43, Comprising polyolefin and wax were prepared sion compared with the nonhydrolyzed interpolymer primer by thoroughly blending the ingredients identified below in the under the test cond tions of the Instron tester. The preferred indicated proportions; mterpolyrners contain from about 15 to about 30 percent by weight units derived from the ester monomer. MM I It will thus be seen that the invention accomplishes its obects and while it has been herein disclosed by reference to the Ehylenwinylaceme coplymu (72% details of preferred embodiments, it is to be understood that elhylemzsq vinylamm, such disclosure [5 intended in an illustrative, rather than a 70% 60% 50% limiting sense, as it is contemplated that various modifications i range 150L155 40% 50% in the materials and method steps will readily occur to those skilled in the art, within the spirit of the invention and the The hydrolyzed interpolymer of example 13 was reacted scope of the appended claims. with tetramethylene glycol toluene diisocyanate by admixture All percentages given herein are by weight unless otherwise therewith in the proportion of 10 parts of a 6% toluene solution of the interpolymer and 1 part of a 46% toluene solution of the isocyanate. The isocyanate-reacted primer was coated onto glassine and aluminum foil respectively at a coating weight of 0.3 lb./ream to provide primed substrates. Each of the hot melt compositions was coated onto each of the primed substrates at a hot melt temperature ranging from 400 F. to 425 F. Here, the control was provided by coating the same hot melt compositions on the same substrates in exactly the same manner with the exception that no primer was used. After cooling, each structure was tested for bond strength with the following results:

Ethylene-vinyl acetate copolymer of 67 percent by weight of ethylene and 33 percent by weight of vinyl acetate was hydrolyzed by the aforedescribed hydrolysis procedure to provide a 13 percent hydrolyzed ethylene-vinyl acetate interpolymer primer having the following composition:

7: 1 k Vinyl Vinyl Hydrolysis Ethylene Acetate Alcohol ElVAc E/VA The hydrolyzed interpolymer was coated onto K Cellophane, glassine, and aluminum foil respectively and thereafter extrusion coated with polyethylene at a melt temperature of 500 F.

The bond strengths obtained and that of a polyethyleneimine control were as follows:

BOND STRENGTH g./in.

Substrate 24 Hours 3 Weeks K Cellophane 200 170 Glassine 300 230 indicated.

We claim:

1. A method of adhering a hot melt olefin polymer coating composition as a film to a substrate wherein the coating composition contains an olefin polymer susceptible to oxidation or degradation at the elevated melt temperature required to secure the coating to the substrate by direct extrusion from a melt, which method comprises applying to the surface of the substrate a primer comprising a hydrolyzed copolymer of an olefin monomer and a vinyl alcohol ester monomer in which the ratio on a weight basis of hydrolyzed ester to olefin is at least 1:70 so as to coat the substrate surface, and applying the olefin polymer coating material to the primed surface from a hot melt significantly below the oxidation and degradation temperatures of said olefin polymer coating composition, said hot melt temperature being no higher than 560 F., to form a tightly adherent film thereon.

2. The method of claim 1 wherein said coating material is selected from the class consisting of polyethylene, polypropylene and copolymers and terpolymers of ethylene or propylene with each other or with a monomer selected from the class consisting of vinyl alcohol and its esters, acrylic acid and substituted acrylic acid and its esters, vinyl chloride, lower olefins in the C to C range, and halogen containing lower olefins, and ionomers of said copolymers and terpolymers.

3. The method of claim 1 wherein the resulting product has a bond tensile strength between coating and substrate which is at least 50 grams per inch better than the bond resulting from use of the unhydrolyzed counterpart of said hydrolyzed copolymer in lieu of the hydrolyzed copolymer of the primer.

4. The method of claim 1 wherein said copolymer is cross linked with an isocyanate in an amount sufficient to improve the chemical resistance of the bond.

5. The method of claim 1 wherein said copolymer contains between 8 and 50 percent by weight of units of said ester and the remainder being said olefin.

6. The method of claim 1 in which said primer is applied in an amount of 0.1 to 1.5 pounds of the hydrolyzed copolymer per 3000 square feet of substrate surface.

7. The method of claim 1 wherein the olefin polymer coating material is applied in a thickness of up to about 2 mils.

8. The method of claim 1 wherein the olefin polymer coating material is polyethylene applied by extruding from the hot melt'at a temperature in the range of from about 375 F to about 560 F.

9. The method of claim 1 wherein said primer is applied to the surface of the substrate in the proper amount creating a bond strength of at least about 200 grams per inch on the Instron tensile tester.

ldtwt 3 6lfi,l9J Dated October 26, 1971 luvcntorflfl m E erhglzgr "Lt is vorLilitd that error appears in the abovc-idcntifiod potent and that said Letters Patent; are hereby corrected as shown below:

T Column 4, line 21, delete "100" and substitute 1.

Column 5, line 9, delete "branches" and substitute -branched-.

Column 10, line 16, first column under "3 weeks" insert O.

Column 10, line 37, delete "coated".

Column 15, line 19, delete "coplymer" and substitute copolymer.

Signed and sealed this 28th day of November 1972.

(SEAL) Attest:

EDWARD M.FLJ:JTCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents 

2. The method of claim 1 wherein said coating material is selected from the class consisting of polyethylene, polypropylene and copolymers and terpolymers of ethylene or propylene with each other or with a monomer selected from the class consisting of vinyl alcohol and its esters, acrylic acid and substituted acrylic acid and its esters, vinyl chloride, lower olefins in the C2 to C6 range, and halogen containing lower olefins, and ionomers of said copolymers and terpolymers.
 3. The method of claim 1 wherein the resulting product has a bond tensile strength between coating and substrate which is at least 50 grams per inch better than the bond resulting from use of the unhydrolyzed counterpart of said hydrolyzed copolymer in lieu of the hydrolyzed copolymer of the primer.
 4. The method of claim 1 wherein said copolymer is cross linked with an isocyanate in an amount sufficient to improve the chemical resistance of the bond.
 5. The method of claim 1 wherein said copolymer contains between 8 and 50 percent by weight of units of said ester and the remainder being said olefin.
 6. The method of claim 1 in which said primer is applied in an amount of 0.1 to 1.5 pounds of the hydrolyzed copolymer per 3000 square feet of substrate surface.
 7. The method of claim 1 wherein the olefin polymer coating material is applied in a thickness of up to about 2 mils.
 8. The method of claim 1 wherein the olefin polymer coating material is polyethylene applied by extruding from the hot melt at a temperature in the range of from about 375* F. to about 560* F.
 9. The method of claim 1 wherein said primer is applied to the surface of the substrate in the proper amount creating a bond strength of at least about 200 grams per inch on the Instron tensile tester.
 10. The method of claim 9 including the step of permitting the coated substrate to age at ambient conditions for 24 hours prior to testing for said tensile strength.
 11. The method of claim 9 including the step of permitting the coated substrate to age at ambient conditions for 3 weeks prior to testing for said tensile strength.
 12. The method of claim 1 wherein the olefin monomer of said hydrolyzed copolymer is a C2 to C8 olefin.
 13. The method of claim 1 wherein said hydrolyzed copolymer is a hydrolyzed copolymer of vinyl acetate and ethylene containing from about 15 percent to about 30 percent by wEight vinyl acetate units, with from about 3 percent to about 40 percent of the acetate groups hydrolyzed to hydroxyl groups.
 14. The method of claim 1 wherein the hydrolyzed copolymer is an interpolymer having the structure of (C2H4)x (C2H3OH)y (C2H3OCOCH3)z wherein x, y, and z are positive rational numbers greater than zero, the ratio on a weight basis of x to y being greater than about 5:1, and the ratio of x to z being within the range of from about 1:1 to about 10:1, and said olefin polymer is a member of the group consisting of polyethylene, polypropylene, copolymers of ethylene and propylene with each other or with vinyl acetate, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, isobutyl acrylate, vinyl chloride, methyl methacrylate, tetrafluoroethylene, and butene-1 respectively, ionomers of ethylene-acrylic acid copolymers, and ethylene-ethyl acrylate-acrylic acid terpolymers, wherein all of said copolymers have a predominant proportion of olefinic monomer, said film having a thickness of from about 0.1 to about 10 mils and being extruded at a temperature taken at the adapter or die lands of the extruder of less than about 560* F.
 15. The method of claim 14 wherein the polyolefin film is polyethylene.
 16. The method of claim 14 wherein the polyolefin film is polypropylene.
 17. The method of claim 14 wherein the polyolefin film is a copolymer of ethylene and vinyl acetate.
 18. The method of claim 14 wherein the polyolefin film is an ionomer of ethylene and acrylic acid.
 19. A method of adhering a polyolefin film to a packaging substrate to provide an improved polymer coated product comprising: a. coating a packaging substrate with the reaction product of i. an interpolymer having the structure of (C2H4)x (C2H3OH)y (C2H3OCOCH3)z wherein x, y, and z are positive rational numbers greater than zero, the ratio on a weight basis of x to y being within the range of from about 5:1 to about 70:1 , and the ratio of x to z being within the range of from about 1:1 to about 10:1, and ii. an organic isocyanate, b. extruding onto said coated substrate a film which is a member of the group consisting of polyethylene, polypropylene, copolymers of ethylene and propylene with each other or with vinyl acetate, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, isobutyl acrylate, vinyl chloride, methyl methacrylate, tetrafluoroethylene, and butene-1 respectively, ionomers of ethylene-acrylic acid copolymers and ethylene-ethyl acrylate-acrylic acid terpolymers, wherein all of said copolymers have a predominant proportion of olefinic monomer, said film having a thickness of from about 0.1 to about 10 mils and being extruded at a temperature taken at the adapter or die lands of the extruder of less than about 560* F.
 20. The method of claim 19 wherein the polyolefin film is polyethylene.
 21. The method of claim 19 wherein the polyolefin film is polypropylene.
 22. The method of claim 19 wherein the polyolefin film is a copolymer of ethylene and vinyl acetate.
 23. The method of claim 19 wherein the polyolefin film is an ionomer of ethylene and acrylic acid copolymer.
 24. The method of claim 19 wherein the organic isocyanate is selected from the group consisting of alkyl isocyanates, aryl isocyanates, alkyl aryl isocyanates, aryl-alkyl isocyanates, polyalkylene isocyanates, and adducts of an organic isocyanate with aliphatic triols, diols, or mixtures thereof.
 25. The method of claim 19 wherein the organic isocyanate is polymethylene polyphenyl isocyanate.
 26. The method of claim 19 wherein the organic isocyanate is a triol aryl isocyanate.
 27. The method of claim 19 wherein the oRganic isocyanate is a diol aryl isocyanate.
 28. A method of adhering a polyethylene film to a packaging substrate to provide an improved polymer coated product comprising: a. coating a flexible substrate with an interpolymer having the structure of (C2H4)x (C2H3OH)y (C2H3OCOCH3)z wherein x, y, and z are positive rational numbers greater than zero, the ratio on a weight basis of x to y being within the range of from about 30:1 to about 70:1 and the ratio of x to z being within the range of from about 2:1 to about 8:1, b. extruding onto said coated substrate an olefin polymer film having a thickness of from about 0.1 to about 10 mils. in which the polymer is selected from the class consisting of polyethylene and a copolymer of ethylene and vinyl acetate, said film being extruded at a temperature taken at the adapter or die lands of the extruder of less than about 525* F.
 29. A method of adhering a polyolefin film to a flexible substrate to provide an improved polymer coated product comprising: a. coating a flexible substrate with the reaction product of (i) an interpolymer having the structure of (C2H4)x (C2H3OH)y (C2H3OCOCH3)z wherein x, y, and z are positive rational numbers greater than zero, the ratio on a weight basis of x to y being within the range of from about 30:1 to about 70:1 , and the ratio of x to z being within the range of from about 2:1 to about 8:1, and (ii) an isocyanate selected from the group consisting of alkyl isocyanates, aryl isocyanates, alkyl-aryl isocyanates, aryl-alkyl isocyanates, polyalkylene isocyanates, and adducts of an organic isocyanate with aliphatic triols, diols, or mixtures thereof, b. extruding onto said coated substrate an olefin polymer film having a thickness of from about 0.1 to about 10 mils. in which the polymer is selected from the class consisting of polyethylene and a copolymer of ethylene and vinyl acetate, said film being extruded at a temperature taken at the adapter or die lands of the extruder of less than about 525* F.
 30. A packaging material laminate comprising a substrate layer of packaging material, a primer on the surface of said substrate comprising a hydrolyzed copolymer of an olefin monomer and a vinyl alcohol ester monomer in which copolymer the ratio on a weight basis of hydrolyzed ester to olefin is at least about 1: 70, and a coating adhered to and fused with said primer, said coating consisting essentially of an extruded film of unoxidized and undegraded olefin polymer susceptible to oxidation deterioration at its normal extrusion temperature applied as a melt to said primer.
 31. A composite flexible packaging material structure which comprises in intimate joined lamination: a. a flexible substrate layer, b. an intermediate adhesion promoting layer of an interpolymer having the structure of (C2H4)x (C2H3OH)y (C2H3OCOCH3)z wherein x, y, and z are positive rational numbers greater than zero, the ratio on a weight basis of x to y being within the range of from about 5:1 to about 70:1, and the ratio of x to z being within the range of from about 1:1 to about 10:1, and c. a tightly adhered layer over said intermediate adhesion promoting layer of an extruded film having a thickness of from about 0.1 to about 10 mils, said film being selected from the group consisting of polyethylene, polypropylene, copolymers of ethylene and propylene with each other or with vinyl acetate, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, isobutyl acrylate, vinyl chloride, methyl methacrylate, tetrafluoroethylene, anD butene-1, respectively, ionomers of ethylene-acrylic acid copolymers and ethylene-ethyl acrylate-acrylic acid terpolymers, wherein all of said copolymers have a predominant proportion of olefinic monomer, said film being extruded onto said intermediate adhesion promoting layer at a temperature at the adapter or die lands of the extruder of less than about 560* F.
 32. The composite structure of claim 31 wherein the adhered layer over said intermediate adhesion promoting layer is polyethylene.
 33. A composite flexible packaging material structure which comprises in intimate joined lamination: a. a flexible substrate, b. an intermediate adhesion promoting layer of at least 0.1 lb. per 3,000 sq. ft. of said substrate surface of the reaction product of (i) an interpolymer having the structure of (C2H4)x (C2H3OH)y (C2H3OCOCH3)z wherein x, y and z are positive rational numbers greater than zero, the ratio on a weight basis of x to y being within the range of from about 30.1 to about 70:1, and the ratio of x to z being within the range of from about 2:1 to about 8:1, and (ii) an isocyanate selected from the group consisting of alkyl isocyanates, aryl isocyanates, alkyl-aryl isocyanates, aryl-alkyl isocyanates, polyalkylene isocyanates, and adducts of an organic isocyanate with aliphatic triols, diols, or mixtures thereof, and c. a tightly adhered film over said intermediate adhesion promoting layer of from about 0.1 to about 10 mils, said film being selected from the group consisting of polyethylene, polypropylene, copolymers of ethylene and propylene with each other or with vinyl acetate, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, isobutyl acrylate, vinyl chloride, methyl methacrylate, tetrafluoroethylene, and butene-1 respectively, ionomers of ethylene-acrylic acid copolymers and ethylene-ethyl acrylate-acrylic acid terpolymers wherein all of said copolymers have a predominant proportion of olefinic monomer, said film being extruded onto said intermediate adhesion promoting layer at a temperature at the adapter or die lands of the extruder of less than about 560* F. 